1、American Petroleum Institute LABOMTORY ANALYSIS OF PETROLEUM INDUSTRY WASTEWATERS ARRANGING FOR ANALYSIS AND UNDERSTANDING LABORATORY REPORTS REGULATORY AND SCENTIFIC AFFAIRS PUBLICATION NUMBER 4694 DECEMBER 1999 American Petroleum Institute American Petroleum Institute Environmental, Health, and Sa
2、fety Mission and Guiding Principles MISSION The members of the American Petroleum Institute are dedicated to continuous efforts to improve the compatibility of our operations with the environment while economically developing energy resources and supplying high quality products and services to consu
3、mers. We recognize our responsibility to work with the public, the government, and others to develop and to use natural resources in an environmentally sound manner while protecting the health and safety of our employees and the public. To meet these responsibilities, API members pledge to manage ou
4、r businesses according to the following principles using sound science to prioritize risks and to implement cost-effective management practices: PRINCIPLES 0 To recognize and to respond to community concerns about our raw materials, products and operations. To operate our plants and facilities, and
5、to handle our raw materials and products in a manner that protects the environment, and the safety and health of our employees and the public. To make safety, health and environmental considerations a priority in our planning, and our development of new products and processes. To advise promptly, ap
6、propriate officials, employees, customers and the public of information on significant industry-related safety, health and environmental hazards, and to recommend protective measures. To counsel customers, transporters and others in the safe use, transportation and disposal of our raw materials, pro
7、ducts and waste materials. To economically develop and produce natural resources and to conserve those resources by using energy efficiently. To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes and waste m
8、aterials. To commit to reduce overall emission and waste generation. To work with others to resolve problems created by handling and disposal of hazardous substances from our operations. To participate with government and others in creating responsible laws, regulations and standards to safeguard th
9、e community, workplace and environment. To promote these principles and practices by sharing experiences and offering assistance to others who produce, handle, use, transport or dispose of similar raw materials, petroleum products and wastes. Laboratory Analysis of Petroleum Industry Wastewaters Arr
10、anging for Analysis and Understanding Laboratory Reports Regulatory and Scientific Affairs API PUBLICATION NUMBER 4694 PREPARED UNDER CONTRACT BY: TISCHLEKOCUREK ROUND ROCK, TEXAS DECEMBER 1999 American Petroleum I Institute FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE.
11、 WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED. API IS NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS, WAC- TURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMPLOYEES, AND OTHERS EXPOSED, CONCERNING HEALTH AND SAFETY RISKS
12、 AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONS UNDER LOCAL, STATE, OR FEDERAL LAWS. NOTHING CONTAINED IN ANY API PUBLICATION IS TO BE CONSTRUED AS GRANTING ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THE MANU- FACTURE, SALE, OR USE OF ANY METHOD, APPARATUS, OR PRODUCT COV- ERED BY LETTERS PATEN
13、T. NEITHER SHOULD ANYTHING CONTAINED IN ITY FOR INFRINGEMENT OF LETTERS PATENT. THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- All rights resewed. No part of this work may be reproduced, stored in a retrieval system, or transmitted by any means, electronic, mechanical, photocopying.
14、 recording. or otherwise, without prior written permission from the publisher: Contact the publisher; API Publishing Services. 1220 L Street, N.W, Washington, D.C. 20005. Copyright D 1999 American Petroleum Institute STD-APIIPETRO PUBL 4b94-ENGL 1999 0332290 Ob192Bb 089 ACKNOWLEDGMENTS THE FOLLOWING
15、 PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT: API STAFF CONTACT Roger Claff, Regulatory and Scientific Affairs MEMBERS OF THE WATER TECHNOLOGY TASK FORCE Robert Goodrich, Exxon Research and Engineering Company, Chairpers
16、on David Pierce, Chevron Research and Technology Company, Vice Chairperson Terrie Blackburn, Williams Pipeline Company Deborah Bolton, Chevron Products Marketing Company Vic Carlstrom, Mobil Exploration and Production US Incorporated Leanne Kunce, BP Oil Company Jim Mahon, FINA Company William Marti
17、n, ARC0 Products Company Gary Morris, Mobil Technology Company Arnold Marsden, Jr., Equiva Services LLC Barbara Padlo, Amoco Research Center Gerry Sheely, Marathon Ashland Petroleum LLC Paul Sun, Equilon Enterprises LLC STD-API/PETRO PUBL 4b94-ENGL 3999 I 0732290 0639287 TI5 Preface The American Pet
18、roleum Institutes (APIs) Health and Environmental Sciences Department, through the API Water Technology Task Force, has conducted a multi-year research program to identify and evaluate practical and environmentally sound technologies for watedwastewater treatment for petroleum facilities. The Task F
19、orce has also sponsored work that will help petroleum facilities and government agencies to improve treatment efficiencies to change and comply with regulations. The results of this program are intended to inform decision-makers on appropriate treatment alternatives for individual petroleum manufact
20、uring or distribution facilities. The Task Force has sponsored and published a significant amount of work in prior years on handling and treating petroleum waters. A listing of some key published reports and guidance documents is summarized below. The goal of this report is to assist individual petr
21、oleum facilities to understand, interpret, and arrange for the proper laboratory analyses of petroleum industry wastewaters, whether done by in-house staff or through another resource. The report should be applicable to several types of petroleum facilities, including refineries, marketing and pipel
22、ine terminals, production facilities, and underground storage tank sites. This report is very comprehensive; it covers development of cost-effective analytical plans, selecting a laboratory, key considerations in evaluating laboratory reports, detection limits, QNQC, available resources, and statist
23、ical calculations. The report is structured in a tiered fashion, with the most critical information, in a simple format, presented first. More detailed material covering specialized topics follows. Case studies, sample laboratory reports and reviews, and data calculations are provided to illustrate
24、the material on this complex but necessary topic of laboratory report review and assessment. In some situations, given stringent NPDES monitoring requirements, the cost implications of erroneous laboratory data or poorly prepared laboratory reports can be tens to hundreds of thousands of dollars fro
25、m fines, investigation costs, follow-up sampling and analysis, etc., not to mention publicity implications. Through this report, the reader will gain useful information and insight that may help prevent realizing these implications. The Task Force gratefully acknowledges and appreciates the fine wor
26、k performed by TishlerKocurek, Round Rock, Texas, in preparing this comprehensive study. Other Studies Sponsored by the Water Technology Task Force Publ. 4664 Mixing Zone Modeling and Dilution Analysis for Water- Quality-Based NPDES Permit Limits, April 1998. Publ. 4665 Analysis and Reduction of Tox
27、icity in Biologically Treated Petroleum Product Terminal Tank Bottoms Water, April 1998. Publ. 1612 Guidance Document for Discharging of Petroleum Distribution Terminal Effluents to Publicly Owned Treatment Works, November 1996. Publ. 4581 Evaluation of Technologies for the Treatment of Petroleum Pr
28、oduct Marketing Terminal Wastewater, June 1993. Publ. 4582 Comparative Evaluation of Biological Treatment of Petroleum Product Terminal Wastewater by the Sequencing Batch Reactor Process and the Rotating Biological Contactor Process, June 1993. Publ. 4602 Minimization, Handling, Treatment, and Dispo
29、sal of Petroleum Product Terminal Wastewaters, September 1994. Publ. 4606 Source Control and Treatment of Contaminants Found in Petroleum Product Terminal Tank Bottoms, August 1994. Abstract A guidance manual is presented by the American Petroleum Institute (API) to assist in arranging for and under
30、standing laboratory analysis of petroleum industry wastewaters. The manual is designed for environmental coordinators, managers, corporate staff, field personnel, and others who must address environmental compliance reporting and regulatory issues. This manual is applicable to wastewaters from petro
31、leum refining, marketing and pipeline terminals, underground storage tank cleanups, and petroleum production facilities. Guidance and information are provided for setting data quality objectives; planning analyses; selecting a laboratory; and reviewing laboratory reports, detection and quantificatio
32、n limits, quality assurance/quality control practices, method references, method-defined analytes, and statistical calculations. The manual contains information on two levels: The first presents the most critical information in a simple format that can be read quickly, and the second discusses addit
33、ional detail and related topics. Examples of case studies, laboratory reports, and data calculations are given throughout the manual. Checklists are provided to help users understand, plan, and review laboratory data. STD*API/PETRO PUBL 4694-ENGL 1979 H 0732290 Ob19290 SOT H Contents Introduction Ty
34、pes of Wastewater Covered Purpose of This Manual Whats in This Manual Overview of Manual Quick Start 1 11 11 111 V . Part I Essential Information Chapter 1 Setting Objectives 1-1 Chapter 2 Planning Analyses 2-1 Methods Specified by Regulatory NPDES-Approved Methods Requirements at 40 CFR 136 Alterna
35、te Methods SW-846 Methods Detection and Quantification Limits Matrix Interferences Quality Assurance/Quality Control Common Terms Spikes Duplicates and Replicates Blanks Outlining QNQC Requirements with the Laboratory Developing an Analytical Schedule 2-2 2-2 2-2 2-5 2-8 2-8 2-12 2-14 2-15 2-15 2-17
36、 2-17 2-17 2-19 Chapter 3 Selecting a Laboratory 3-1 Required Analyses In-House or Commercial Laboratory Capabilities 3-1 3-2 3-2 STD-APIIPETRO PUBL 4bSY-ENGL L999 Staffing Equipment Subcontracting of Analyses Support Services Sample Containers and Preservatives Sampling Personnel Recordkeeping and
37、Reporting Archiving Samples Reputation and Size costs Site Visit Evaluating Laboratory Performance with Test Samples Getting Help from Consultants 3-2 3-3 3-3 3 -4 3 -4 3 -4 3-5 3 -6 3 -6 3-7 3-8 3-10 3-1 3 Chapter 4 Reviewing Laboratory Reports 4-1 Report Contents Reviewing Reports Checking the Bas
38、ics Problems Requiring Immediate Response Permit Limit Exceeded Wrong Analytical Method Holding Time Exceeded Improper Preservative or Container Wrong Reporting Limits Missing Sample Missing Analyte Are the Results Reasonable? Method-Defined Analytes Detection and Quantification Limits Quality Assur
39、ance/Quality Control Sample Results 4-1 4-6 4-6 4-7 4-9 4-9 4-9 4-1 0 4-1 2 4-1 2 4-1 3 4-14 4- 14 4-16 4-1 8 4-1 8 Part II Additional Detail and Special Topics Chapter 5 Detection and Quantification Limits 5-1 Definitions Application and Interpretation 5-1 5-3 STD-APIIPETRO PUBL 4694-ENGL 1999 = 07
40、32290 ObL9292 382 m Chapter 6 Chapter 7 Chapter 8 Quality Assurance/Quality Control Common Terms Spikes Standard Solutions Matrix Spike Surrogate Spike Internal Standard Spike Isotope Dilution Spike Method of Standard Addition Spike Recovery Correction Duplicates Replicates Blanks Requirements in An
41、alytical Methods Laboratory Requirements Checking Performance with QNQC Criteria Method References NPDES Method References U.S. Environmental Protection Agency American Public Health Association American Society for Testing and Materials Association of Official Analytical Chemists US. Geological Sur
42、vey Proprietary Methods S W-846 Method-Defined Analytes Biochemical Oxygen Demand Chemical Oxygen Demand Total Organic Carbon Oil and Grease Total Petroleum Hydrocarbons Phenols Total Solids Total Suspended Solids Total Dissolved Solids Surfactants Whole Effluent Toxicity 6- 1 6- 1 6- 1 6-2 6-2 6-4
43、6-5 6-6 6-6 6-6 6-7 6-8 6-8 6-9 6-10 6-12 7-1 7-1 7-1 7-2 7-2 7-2 7-3 7-3 7-3 8-1 8-1 8-2 8-3 8-3 8-4 8-4 8-5 8-5 8-5 8-6 8-6 STD.API/PETRO PUBL 4b94-ENGL 1999 0732290 Ob19293 219 Chapter 9 Statistical Calculations Data Distributions Precision Standard Deviation Coefficient of Variation Relative Sta
44、ndard Deviation Relative Percent Difference Tolerance Limit Confidence Limit Precision Statements Bias Accuracy and Recovery Relationships Among Precision, Bias, and Accuracy Outliers Nondetects and Censored Data Substitution Median Modified Delta-Lognormal Distribution Cohens Method EPA Method Dete
45、ction Limit Part 111 References and Acronyms References Acronyms and Abbreviations 9-1 9-1 9-3 9-4 9-5 9-5 9-5 9-6 9-7 9-7 9-8 9-1 1 9-12 9-1 3 9-14 9-1 5 9-1 5 9-15 9-16 9-16 Part IV Checklists Checklists STD*API/PETRO PUBL 4b94-ENGL 3999 0732290 Ob39294 355 Table 1-1 2- 1 2-2 2-3 2-4 2-5 2-6 2-7 3
46、-1 3 -2 3-3 4- 1 4-2 4-3 4-4 4-5 Page Example of General DQO Statements for Analytical Data 1-3 Description of Analytical Specifications at 40 CFR 136 2-3 Analytical Method References at 40 CFR 136 2-4 Examples of Water Quality Criteria that are Below 2-9 Analytical Method Detection and Quantificati
47、on Capabilities Example Elements of Quality Control Program 2-1 5 Example Elements of Quality Assurance Program 2-15 Common Types of Sample Spikes 2-16 Sample Questions on QNQC for Initial Discussion 2-1 8 with Laboratory Example Elements of a Good Laboratory 3 -6 Recordkeeping System Example Items
48、that may be Included in an 3 -9 Onsite Laboratory Evaluation Examples of Sample Types Used to Evaluate 3-1 1 Laboratory Performance Items Typically Included in Analytical Laboratory Report 4-3 Sample Questions to Perform Initial Review of 4-6 Laboratory Report Required Containers, Preservation Techn
49、iques, 4-11 and Holding Times from 40 CFR 136 for Selected Analytes Examples of Alternate Names for Some Common 4-13 Wastewater Analytes Example of Notations Qualifying Analytical Results 4-16 Table 4-6 5-1 6- 1 6-2 6-3 6-4 6-5 6-6 6-7 6-8 9- 1 9-2 9-3 Examples of Method-Defined Analytes for Wastewater Definitions of Terms Commonly Used in Reference to Detection and Quantification Limits Example of Analytes Used for Matrix Spikes for Organic Analyses Example of Analytes Used for Surrogate Spikes for Organic Analyses Example of Analytes Used for Internal Standard Spikes for O
